Molecules 2015, 20, 7528-7557; doi:10.3390/molecules20057528 OPEN ACCESS molecules ISSN 1420-3049 www.mdpi.com/journal/molecules Review Recent Developments in the Suzuki-Miyaura Reaction: 2010–2014

Irene Maluenda and Oscar Navarro *

Department of Chemistry, University of Sussex, Brighton BN1 9QJ, UK

* Author to whom correspondence should be addressed; E-Mail: [email protected]; Tel.: +44-1273-678734; Fax: +44-1273-876687.

Academic Editor: John Spencer

Received: 17 March 2015 / Accepted: 13 April 2015 / Published: 24 April 2015

Abstract: The Suzuki-Miyaura reaction (SMR), involving the coupling of an organoboron reagent and an organic halide or pseudo-halide in the presence of a or catalyst and a , has arguably become one of most utilized tools for the construction of a C-C bond. This review intends to be general account of all types of catalytic systems, new coupling partners and applications, including the literature between September 2010 and December 2014.

Keywords: Suzuki-Miyaura; palladium; nickel; N-heterocyclic carbene; phosphine; polymerization

1. Introduction

Since its discovery in 1979 [1], the Suzuki-Miyaura reaction (SMR) [2–5], involving the coupling of an organoboron reagent and an organic halide or pseudo-halide in the presence of a palladium or nickel catalyst and a base, has arguably become one of most utilized tools for the construction of a C-C bond. The reaction follows an transmetallation catalytic cycle that benefits from the use of electron-donating, sterically demanding which promote first and last steps [2]. Clear advantages over other palladium-catalyzed cross-coupling reactions [5] include: (i) mild reaction conditions; (ii) ready availability of organoboron reagents, which also are inert to water and related , as well as oxygen, and generally thermally stable; (iii) tolerant toward various functional groups; and (iv) low toxicity of starting materials and by-products [6]. These features have allowed researchers to utilize it in a wide variety of applications, from synthesis to the development of polymeric materials. Due to its impact in such a variety of fields, , Molecules 2015, 20 7529 together with Richard F. Heck and Ei-Ichi Negishi, was awarded in September 2010 the “for palladium-catalyzed cross couplings in ”. Since then, excellent and thorough reviews covering specific aspects of this reaction have been published: a historical account [7], and reviews focusing on Ni-catalyzed reactions [8], nanocatalysts [9], preformed Pd catalysts [10], sulphur-containing ligands [11,12], and the coupling of polyhalogenated heteroarenes [13]. This review intends to be a more general account of all types of catalytic systems, new coupling partners and applications, including the literature between September 2010 and December 2014. It is worth pointing out that a Scopus search on the topic “Suzuki coupling” lead to more than 3000 articles during that period; therefore, only a selection of the most significant developments and applications of the SMR are presented in here. In addition and for simplicity, details on the specifics of the reaction conditions (base, , temperature) have been omitted unless any of those factors where determinant to the outcome, focusing mostly in coupling partners, ligands, metals and products.